Pesticide emulsions containing an oxyethylated oxypropylated glycerine



PESTICIDE EMULSIONS CONTAINING AN OXY- ETHYLATED OXYPROPY LATED GLYCERINE Willard H. Kirkpatrick, Sugar Land, and Virgil L. Scale, Houston, Tex.,',assignors to Visco. Products Company, Houston, Tex., a corporation of Delaware No Drawing. Application December 7, 1953 Serial N 0. 396,771

8' Claims. (Cl. 167-43) This invention relates to emulsions, especially oil-inwater emulsions, and more particularly emulsions containing at least four components, one of said components being water, the second of said components being oil, the

Pa tented Feb. 24,1959

the practice of the invention isprobablya trihydroxy' polyoxyethylene-polyoxypropylene ether of glycerine con'-' taining an oxyethylated oxypropylene chain linked through an oxygen atom to each carbon atom of the glycerine molecule and having a terminal hydroxyl group at the end of each oxyethylene chain. The average number of 1 oxypropylene groups (e.- g., oxy-1,2-propylene) injeach fying agent. 'There" seemitd'be littledoubt that'the' chain is preferably at least 27 and not more than 42,

and the average number of oxyethylene groups in each chain is preferably at least 14 and not greater -than' 45.

I It will. be understood, however, that the invention is'not limited to any particular manner of defining the emulsipreferred emulsifying agent is a complex mixture, al-

though it mightlbe possible to'pre'pare individual com-' ponents of the mixture which would be useful in the third of said components being an emulsifying agent and the fourth of said components being an active esexample, to kill pests, to destroy fungi or to destroy vegesential ingredient employed for a specific purpose,- for 2 tation. If'the fourth component is a toxic agent adapted to kill pests, the resultant composition is called a pesticide. If the fourth component is a toxic agent adapted to kill fungi, the resultant composition is called a fungicide, and if the fourth component is a toxic agent adapted to kill vegetation or to defoliate vegetation, the resultant composition is called a herbicide.

Many emulsions of oil-in-water which contains three components, namely oil, water and an emulsifying agent, are relatively unstable in the presence of a fourth com ponent, such as those previously mentioned.

One of the ob ects of the present invention is to provide new and improved emulsions containing at least four components which are unusually stable.

Another object of the invention is to provide a new and improved method for preparing emulsions of the type described. Other objects will appear hereinafter.

. -In accordance with the invention these objects are accomplished by emulsifying oil, water and at ,least oneother component, for example, a toxic agent, with an emulsifying agent which is an oxyethylated-oxypropylated glycerine wherein polyoxypropylene chains, preferably polyoxy-LLZ-propylene chains, are attached to the glycerine nucleus, and polyoxyethylene chains are in turn attached to said polyoxypropylene chains, the terminal; groups being hydroxyl groups of the polyoxyethylene chains. f

The oxyethylated-oxypropylated glycerine preferred for the practice of the invention is preferably an oxyethylatedoxypropylated glycerine derived by oxypropylating glycerine with 60 to 70 parts by weight of 1,2-propylene oxide per part of glycerine, and then oxyethylating the oxypropylated glycerine with 0.5 to 0.7 part by'weight of ethylene oxide per part of oxypropylated glycerine.

- The oxyethylated-oxypropylated glycerine used in accordance with the invention is preferably a liquid having'a viscosity greater than 30 centistokes at 100 F. It normally contains at least 120 mols of oxyalkylene groups per glycerly group ofwhich about 48 to about 66 mol percent, preferably 5.1% to 60%, is oxy-l,2-propylene-and the remainder is oxyethylene. The kind and number of oxyalkylene groups should preferably besuch that the resultant product is not a solid. Usually, no more than -12,6-oxy- 1,2-propylene groups, nor more than 135 oxypractice of the invention. r

The invention'is concerned with the preparation of emulsions containing at least'four componentsand. not

the method of preparing the emulsifying agent,.but for the sake of completeness, the following example is given to illustrate the preparation of oxyethylated oxypropylated.

glycerine. v a p EXAMPLE I, V l

v I One pound of glycerine and 60 grams of 'analkaline catalyst such as NaOH or KOH was. charged to apressure nettle, with good agitation and proper temperature controlling facilities. This mixture washeated. to 1 20 C. to 150 C. and then 1,2-propyleneoxideadded maintaining a temperature of 120 3 C. to 150? C. and pressure of 25 to 100 pounds per square inch gaugeuntil70 pounds of 1,2-propylene oxide per pound of glycerine was added. Samples were taken when 40, 50, 52 55. and 57 /2, 60, 62%, 65 and pounds of 1,2-propylene oxide per pound of glycerine had been added. 'To each of the above sample 0.35, 0.44, 0.51, 0.57, 0 .62 and 0.65 pounds of ethylene oxide per pound of oxypropylated glycerine base material were added. This gave aseries of 54 samples for testing as emulsifiers:

Each sample was neutralized with glacial acetic acid.

The reaction conditions,'catalyst' and proportionsfofi the reacting components can bevaried. For example, the temperature can be varied but is preferably within the range of C. to C. Other alkaline catalysts and varying proportions of catalyst can be used. Ex amples of other catalysts are sodium methylate, sodium ethylate and other alkali metal alcoholates. The proportion is usually small, e. g., 0.1 to 1.0 percent by weight ofthe total reactants. Catalyst can be added as the re action proceeds. Nitrogen or other inert gas can be used to remove any air or free oxygen from-the reaction vessel prior to the introduction of 1,2-propylene oxide 'or thereafter. The neutralization with glacial acetic acid neutralizes the catalyst-and stopsthe reaction. Other acids such as lactic acid and homologous fatty acids can be used as'neutralizing agents. Less than 0.1% Water should preferably-be present during the reaction.

The oxyet-hylated-oxypropylated glycerine compositions prepared as described in- ExampleI were'employed in the preparation of emulsions and tested asdeseribedin The oxyethylated-oxypropylated glycerine employed in I r 7 "EXAMPL 1 j 1 nem s ha fs sam s vitybf 1.2 was; 7 I

issolving816grams of technical Toxaph i 5 a e by f 462 grams of Varsol.

I 7 cylinder to giyes a. total liqu iwe iw. exterio 1 o te'ri ti sl secondirconcentratel waszprepared by dissolving '015 v poundoiDDI; in 4 p,arts .hy,,volumetoisolyesso 150 ,and..,. 1 part by volume of xylene'sutficient to make one quart,-

ared adding one 'volume of each of -thi resultant concentrates; containing thecome h 'l cyli der; was iny ertedl t z emme ethylene oxide per pound'o'r voxyprlopylated,base. shouldcontain at least}; ,pounclswgij propylene oxide per pound of glycerinee At these values, i v the 'oxyethylated oxypropylated product will contain ap- 7 5 proximately '52 mole of ethylene. oxide per mol of e's of water inagraduatedi- 10 oxide per mol of'glycerinejv K ethylene oxide per mol of'gly'ceri'ne, as heretofore stated, willi 'notexcei'ediap -glycerine. Accordingly, the minimum mols of ethylene oxide per mol of glycerine will be approximately 48 mols of ethylene oxide perjmol of glycerine and preferably will be a minimum'of about 52 molsof ethylene v I EX MPLEiIr r V In order to; commie 16 resultsiohtaihedti111 the; pracvention l'flqunds PO Ber Pound I 7' l Glyeerine r i 13-} 52A. B: I Z A TI PO==1.2-propylene"oxlde; E0=ethylene oxide. A=Ratlng DDT, I V 'B'= RatingToxaph'ene.

NG No emulsification at'lalll I P=Showsxeg slight emulslflcatlon; 7 l v F -sometem sifleatlon but detinitely'need! improvement;

G-Good. t on t Viscosity at 100" I. in centlsto k ee.

an oxyethylated m propyla te g l:. erin V.

in" tea,

From Itheforegoing table,-, it, ,will he seen that the zrya y ed lyee lin -.,9 ,.1 i. V slqn-nmdh s .b miz und rh v p l p yi ne x d c -i:

lie to; mols:0f v propylene. ky a esl ly ines 19 v pt rpp l e W d ha Q k 7 65 pounds of propylene oxide per of ycerinel t At'this propylene oxide contennjm an' addition of'0.3;5, 1 pound; of ethylene oxide. per pound of t oxyp rgpylated The pnnpc tion ihe es ne b e l fe.

these tests 45 the successful emul- I out using lthe. same procedure as: describedi in Example II employing 'as the "oxyethylated-oxypropylatertglycerin? dj glycerine twithi OiG-Sfpart" weight: of de Theiresults are-"given in; then "Fhe degrf Phototeten w ich mea ured? turbidity scattering: "due to colloidal dispersion The? turbidity in mieroam eres; the sm'aller the partiei'e. and the' g'rea'ter fis tlie de ree of inulsifieationl' "Stabili was measured in terms of the number of milliliters settling";

Thea-separation: of oil? from an; emulsion is' highly' un desirable and when this cjcn red thegamounto'fsettlin'g t 7 In th aecompany ng table, thespontaneousemulsioii t rating .The' maximum mols of the=produet==obtained byfirst:reacting oneepartfbywweight' their reactingl teach; part: by weight-k Dig the;

. the oxyethylated xypropylatedyglyce ihe enemas Emco1H-77..-. fair Triton X-100 p OEOPG At1ox1045-A fa Atlox G1256-.- Emcol H77 Triton X-100 EOPG Atlox 1045-11.... is. Atlox G1256 The commercial emulsifying agents employed in the foregoing tests are described below:

Atlox 1045-A is the mixed olcate laurate of polyoxyethylene sorbitol compounds recommended by the manufacturer as an especially suitable emulsifier for DDT- solvent concentrates and other similar toxicants.

Atlox 6-1256 is a mixture of polyoxyethylenesorbitol esters of mixed fatty and resin acids.

Emcol H-77 is a blend of polyhydroxy alcohols incompletely esterified with fatty acids, especially dicarboxylic acids, particularly recommended by the manufacturer as an emulsifier for Chlordane emulsion concentrates of high Chlordane content.

Triton X-100 is a liquid, nonionic surface active agent especially suitable as an emulsifier for insecticides and herbicides and reported to be a polyoxyethylene glycol monoether of an octyl phenol.

The insecticidal concentrates used in the testsconsist of the following formulations:

Insecticide Solvent Insecticide Solvent Ratio Aramite..... Technical Xylene 2 lb. Aramite per gal.

solvent. Chlordane-- Varsol 8 1b. Chlordane per gal. solvent. DDT 80 vol. percent Solvesso 150 2 lb. DDT per gal. oi

vol. percent Tech. Xylene-.- solven Dleldrin.... Technical Xylene 1.51%). Diieldrin per gal.

' so ven 50 wt. percent Xylene wt. percent Llndane. 50 wt. percent Cyclohexnnone.-. 'Ioxephene- Varsol 6 lb. Toxaphene per gal. solvent.

soluble in hydrophillic solvents.

useful as 'a contact insecticide mm.- control of cotton pests,'aphids, and wire-worms.

Toxaphene is a chlorinated camphene employed in. the control of grasshoppers and most of the common cotton pests. 1

Of the solvents employed in the foregoing insecticidal concentrates, only two need special mention. Varsol is a straight petroleum solvent and Solvesso is a highcontent aromatic solvent synthesized from petroleum.

It will be recognized that in the foregoing tests the proportions are such that the resultant emulsions are oil-in-water emulsions. That is to say, the smaller component, namely the oil, forms the discontinuous phase and the larger component, namely the water, forms the continuous phase. In the practice of the invention, the active ingredient which forms the fourth component of the emulsion can be either in the oil or the water phase, depending upon whether it is soluble in oil or water or. can he in both phases, 'if it is soluble in both phases. In most cases, however, where toxic agents are used as the fourth component of the emulsion they are soluble in organic hydrophobe solvents and substantially in- The preferred emulsifying agents are xylene .soluble and also substantially soluble in water. The hydroxyl value (weight percent 0H) as determined by acetylation (sometimes called the acetyl value) is preferably between 0.8 'and 1.80.

The invention is especially advantageous in preparing relatively stable emulsions rapidly and is particularly valuable for the preparation of emulsions containing dif ficultly emulsifiable substances, including, for example, p'esticidal, fungicidal and herbicidal emulsion compositions. 7

The invention is hereby claimed as follows:

1. An oil-in-water emulsion containing oil, water and at least one toxicant component selected from the group consisting of chlorinated camphene, 1,1,l-trichloro-2,2- bis(p-chlorophenyl)ethane, the gamma isomer of benzene hexachloride, Dicldrin, Chlordane and an alkyl aryl sulfite emulsified with an emulsifying agent which is an oxycthylated-oxypropylated glycerine wherein polyoxypropylene chains are attached to the glycerine nucleus and polyoxyethylene chains are in turn attached to said polyoxypropylene chains, the terminal groups being hydroxyl groups of the polyoxyethylene chains, the oxypropylene groups forming 48% to 66% of the total oxyalkylene groups, the oxyalkylated glycerine containing about 83-126 mols of propylene oxide per mol of glycerine and further containing about 48-135 mols of ethylene oxide per mol of glycerine.

2. An oil-in-water emulsion containing oil, water and at least one toxicant component selected from the group consisting of chlorinated camphene, 1,1,l-trichloro-2,2- bis(p-chlorophenyl)ethane, the gamma isomer of benzene hexachloride, Dicldrin, Chlordane and an alkyl aryl sulfite emulsified ,with an emulsifying agent which is an oxyethylated-oxypropylated glycerine derived by oxypropylating glycerine with 60 to 70 parts by weight of 1,2-propylene oxide per part of glycerine and then oxycthylating the oxypropylated glycerine with 0.5 to 0.7 part by weight of ethylene oxide per part of oxypropylated glycerine. I V

3. An oil-in-water emulsion containing oil, water and at least one toxicant'component selected-from the group consisting of chlorinated camphene, 1,1,1-trichloro-2,2- bis(p-chlorophenyl)ethane, the gamma isomer of benzene hexachloride, Dicldrin, Chlordane and an alkyl aryl sulfite emulsified with an emulsifying agent which is an oxyethylated-oxypropylated glycerine wherein polyoxypropylene chains are attached to the glycerine nucleus and polyoxyethylene chains are in turn attached to said polyoxypropylene chains, the terminal groups being hydroxy groups of the polyoxyethylene chains,,the oxypropylene groups forming 48% to 66% of the total,

, glycerine.

" 4'5 Anoil in-wate'r emulsionfontalning oil vlva tef and chlorinated catnphene V emulsified with an 7 emulsifying age'ntiwhich is, an oxyethylated oiiypropylated glyceiine V wherein polyoxygi opylene chains are attached, to the a attached": to said polyoxypropylene' chains, the lte rrninal' groups being hydroxyl groups ofthe polyoxyethyl'ene chains; the oxyp'ropyl'ene {groups fotming 48%fto 66% of: the" total- "oxyalkyle ne g roups j thei'oiiyalkylated" lyj is m a n ns ti el fi m 1 -t f y n oxide per mol' oi glycerine and further containing' 'ahout liains, the terminal groups being hydrpxyl jgigoups; of

the ,pq px a hy i hainsj yp bpyl'eni i li p' forming 48%; to 66% of thermal oxya'lkyl ene groups, 7

the; oxyalkylated' glycerine leontaining about83';-1'2.6"m01s of'pr op' ylene oxide permol' of glyeetine, and further containing about" 52-135 mols' of'ethylene oxide, pir'molioft 6.; oi l-inwater eniul sion oontainingtom water; and the; gamma isomer, offhenzenehexaehloride'l emulsified with an emulsifyingfagent which is" an: oxyethy latedoxyr vr l' di yc r nfl w e ei p tp opylene; cha ns:

ar'e-attachd' to the gl'ycerine' nucleus 'and' polyoxyethylenej chains are in turn attached to said polyoxypropylen'e' chains the termina lfgroups being hyd 'oxyl groups of the p yo ye y neh i e s p opy ne group's term: 7 ing; 48%1 to 66%. ofithe, (total oxyallcyIene,v groups the oxyalkylated glycerine containing about 83-126 mole of propylene oxide per mol ,o'fg'lycerineand further con taining about 52l-1l35'n1ols of, ethylene oxide ief niofof" glycerine'.

7'. An'oikin-water'emuision containingoihwater and Dieldrjn emulsified withemulsifyingagentjiyhiiih is an; oXyethylated-oxypropylated gly'c'e'rine wherein" polyoxypropylene chains are attached to the glycerine nucleus 7 nd p lyo y thylen h in a e n tu attached to said, polyoxypropylene chains, the terminal gpoups being-J31 t droxyl groups of thf iolyoxyifiyl'ene. ohaiiis the'oxypropylenej groups forming, 48% toi 66f%; 0f 'the 'total oxyalkylene, groups; the; 'oxya'lkylated fglyeeninetcontain ingabout 83-126 mols ofiFpropylene, oxide; pel niol of gljieei'inenand furtheneontainiiig't a'houta of ethylene oxide per mol' oflglyce inet 8'. An oil-m-waten emulsion. contal isian oxyethylated-okypnopylatedlglycbii 4 oxypropylene chains areqattacheditofthe 1y and polyoxyethylen'e chains- 'a're-in-t'urn attached to} 'said' E'P Y YP DY a ve i wrmi iah s fi n j bein' 'k wdroxyl groups of the polyoxyethy-lenegchains,the 6Xy1' propylene groups forming; 48% 'to66%l=' ofjthejtotal oxyalkylene groups, the oxyallq lated, glycerinecontain- 30 h Re ferences Cited in the fil'e'of"this"patet1t';' Q 7 '7 N ED S A ES- 2,447,475 Kaberget ai. H...-.. Aug,- L'l-',;,1948 1 2,521,318 Wohlers; Sliptiv 5, 1950 35 2,674,619 Lunsted. '-.4A r; 6;;1954

glycerine-and furthercontainingahout{52'-1'35- molfsfbf thYlhf P pl'ofn'gly l r nefl OTHER REFERENCES Frearz Pesticide Handbook,.;? 4th ed.,YCo1lege{'Sci. PublsL, State College Pa "195.2,,pp. 13,; 1 4 and 134.

UNITED sTATEs PATENT OFFICE CERTIFICATE OF CORRECTION v Patent No. 2 ,8'75 ,128 February 24, 1959 Willard H, Kirkpatrick et al,

Column 1, line 58, for "30 Gentistoke-s" read 300 centistoke-s line 60, for "glycerly" read glyceryl line 66, for moleculU' read molecule column 2, line 28, for "nettle" read kettle line 37,

for 'sample" read samples Signed and sealed this 4th day of August 1959.

(SEAL) Attest:

KARL H. AXLINE I ROBERT C. WATSON Attesting Oflicer 4 Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,875,128 February 24, 1959 Willard H, Kirkpatrick et al.

Column 1, line 58, for "30 centistoke-s" read 300 centistoke-s line 60, for "glycerly" read glyceryl line 66, for "molecult" read molecule I; column 2, line 28, for "nettle" read kettle line 37, for 'fsample" read samples Signed and sealed this 4th day of August 1959.

(SEAL) Attest:

KARL AXLINE ROBERT c. WATSON Attesting Oflicer v Commissioner of Patents 

1. AN OIL-IN-WATER EMULSION CONTAINING OIL, WATER AND AT LEAST ONE TOXICANT COMPONENT SELECTED FROM THE GROUP CONSISTING OF CHLORINATED CAMPHENE, 1,1,1-TRICHLORO-2,2 BIS(P-CHLOROPHENYL)ETHANE, ATHE GAMMA ISOMER OF BENZENE HEXACHLORIDE, DIELDRIN, CHLORDANE AND AN ALKYL ARYL SULFITE EMULSIFIED WITH AN EMULSIFYING AGENT WHICH IS AN OXYETHYLATED-OXYPROPYLATED GLYCERINE WHEREIN POLYOXYPROPYLENE CHAINS ARE ATTACHED TO THE GLYCERINE NUCLEUS AND POLYOXYPROPYLENE CHAINS, THE TERMINAL GROUPS BEING IHYPOLYOXYPROPYLENE CHAINS, THE TERMINAL GROUPS BEING HYDROXYL GROUPS OF THE POLYOXYETHYLENE CHAINS, THE OXYPROPYLENE GROUPS FORMING 48% TO 66% OF THE TOTAL OXYALKYLENE GROUPS, THE OXYLKLATED GLYCERINE CONTAINING ABOUT 83-126 MOLS OF PROPYLENE OXIDE PER MOL OF GLYCERINE AND FURTHER CONTAINING ABOUT 48-135 MOLS OF ETHYLENE OXIDE PER MOL OF GLYCERINE. 